KR101879725B1 - A novel diaminomaleonitrile porphyrin derivative, composition for detecting mercury ion comprising the same and method for detecting mercury ion using the same - Google Patents

Abstract

The present invention provides a novel diaminomaleonitrile porphyrin compound, a composition for detecting mercury ions comprising the same and a method for detecting mercury ions using the same. The diaminomaleonitrile porphyrin compound, the composition for detecting the mercury ions comprising the same and the method for detecting the mercury ions using the same can be usefully used as a mercury ion specific technique in a cation detection field.

Description

TECHNICAL FIELD The present invention relates to a novel diaminomalonitrile porphyrin derivative, a composition for detecting mercury ion containing the same, and a mercury ion detection method using the same. BACKGROUND ART A novel diaminomaleonitrile porphyrin derivative, a composition for detecting mercury ion,

The present invention relates to a porphyrin derivative used for mercury ion detection, and more particularly, to a novel diaminomalonitrile porphyrin compound, a composition for detecting mercury ion containing the same, and a mercury ion detection method using the porphyrin derivative.

In recent years, there has been a growing interest in the detection and quantification of these metals due to the deleterious effects of heavy- and transition-metal (HTM) ions on organisms and the environment. It is known that methyl mercury causes serious diseases in the organs such as sensory system, muscular system, nervous system and the like when humans ingest.

On the other hand, there is a growing interest in the design and synthesis of chemical sensors for metal ions. These chemical sensors are based on metal complex ligands of structures such as crown ether, cryptand and spherand, and various other chemical sensors have been developed have. Nevertheless, there remains a need for the development of efficient new chemical sensors with high selectivity and sensitivity to mercury.

BACKGROUND ART Porphyrin is a macrocyclic compound containing four pyrrole rings as a kind of a compound that constitutes a pigment component that plays an important role in a redox reaction in vivo. Since porphyrin absorbs light of a long wavelength, it is used in photodynamic therapy using a laser. Particularly, in addition to recent developments in the field of organic electronics, porphyrin has been used as a semiconductor material for application of organic devices such as organic transistors and organic solar cells.

Korean Patent Publication No. 10-2012-0081098 (Jul. 18, 2012) Korean Patent Publication No. 10-2013-0103526 (September 23, 2013) Korean Patent Publication No. 10-2010-0075818 (July 05, 2010)

The inventors of the present invention have been studying a high sensitivity sensing technique for detecting mercury ions, and found that diaminomalonitrile porphyrin derivatives react with mercury ions specifically to cause transition of visible light absorption wavelength and decrease of fluorescence (red) It was confirmed that the reaction specificity was excellent and the selectivity to mercury ion was also superior to other cations.

Accordingly, it is an object of the present invention to provide a diaminomalonitrile porphyrin compound, a composition for detecting mercury ion containing the same, and a mercury ion detection method using the same.

According to one aspect of the present invention, there is provided a compound represented by the following formula (5).

[Chemical Formula 5]

According to another aspect of the present invention, there is provided a process for preparing 5- (4'-hydroxymethylphenyl) -15-phenylporphyrin by reacting (i) benzaldehyde, hydroxymethylbenzaldehyde and dipyrromethane; (Ii) oxidizing the hydroxyl group of 5- (4'-hydroxymethylphenyl) -15-phenylporphyrin obtained in step (i) to obtain 5- (4'-formylphenyl) -15-phenylporphyrin; and Iii) reacting 5- (4'-formylphenyl) -15-phenylporphyrin obtained in step (ii) with diaminomalenonitrile to obtain 2-amino-3 - [(5 ', 15'- H, 23'H-porin-5'-yl) -methyleneamino] -2-butenediitrile].

According to another aspect of the present invention, there is provided a composition for detecting mercury ions comprising the above compound.

In one embodiment, the composition for mercury ion detection may comprise tetrahydrofuran as a solvent.

According to another aspect of the present invention there is provided a mercury ion detection method comprising the step of reacting the compound with a sample.

In one embodiment, the mercury ion detection method can use tetrahydrofuran as a solvent, measuring the absorbance at 400-430 nm in a visible light wavelength range, and measuring the fluorescence at a fluorescence wavelength range of 620-710 nm As shown in FIG.

According to another aspect of the present invention, there is provided a mercury ion detection apparatus using the above compound.

In one embodiment, the mercury ion detection apparatus can use tetrahydrofuran as a solvent, measure absorbance at 400-430 nm in a visible light wavelength range, and measure fluorescence at a fluorescence wavelength range of 620-710 nm.

According to the present invention, a mercury ion reacts specifically with a diaminomalonitrile porphyrin derivative to exhibit a red quenching and transition of visible light absorption wavelength (transition from red to yellow) It was confirmed that the specificity was excellent and the detection limit was 1.12 x 10 < ^-8 >

Accordingly, the diaminomalonitrile porphyrin compound of the present invention, the composition for detecting mercury ions and the mercury ion detection method using the same, can be usefully used as mercury ion-specific techniques in the field of cation detection.

1 is a ¹ H NMR spectrum of a compound of formula 5 (DAMN-porphyrin) in CDCl ₃ .
2 is a ¹³ C NMR spectrum of the compound of Chemical Formula 5 in CDCl ₃ .
3 is a MALDI-TOF spectrum of the compound of formula (IV).
4 is a MALDI-TOF spectrum of the compound of formula (5).
Figure 5 shows the effect of various metal ions on the UV-visible light spectrum of the compound of formula 5 (3.33 x 10 ^-7 M) in THF.
6 is a UV-visible light titration spectrum of the compound of Formula 5 (3.33 x 10 ^-7 M) using Hg (NO ₃ ) ₂ in THF solvent.
7 shows the effect of various metal ions on the fluorescence emission spectrum ([lambda] _ex (excitation wavelength) = 407 nm) of the compound of Formula 5 (3.33 x 10 <" ⁷ >
8 is a fluorescence titration spectrum (λ _ex [excitation wavelength] = 407 nm) of the compound of Formula 5 (3.33 × 10 ^-7 M) using Hg (NO ₃ ) ₂ in THF solvent.
Figure 9 is a frontier molecular orbital (LUMO in HOMO) and optimized structure of DAMN-porphyrin, calculated using the B3LYP level of the Density Functional Theory (DFT).

The present invention provides a compound represented by the following formula (5).

[Chemical Formula 5]

(5 ', 15'-diphenyl-21'H, 23'H-porphyrin-5'-yl) -methyleneamino] -2-butene -Methyleneamino] -2-butenedinitrile]} is referred to as' Dia 'in the present specification, and the term " 2-amino-3 - [(5', 15'- diphenyl- Quot; diaminomaleonitrileporphyrin ", " DAMN-porphyrin ", or " DAMNP ".

Porphyrin is an 18 방향 aromatic macrocyclic compound composed of four pyrrole units and four connected carbon atoms in a planar structure, and porphyrin derivatives are natural and synthetic organic pigments, both of which contain a porphyrin ring as part of the structure. A number of porphyrin derivatives exist naturally and are examples of pigments in red blood cells and heme, a cofactor of hemoglobin proteins.

The diaminomalonitrile-based imine materials act as various metal ions and anion sensors.

The diaminomalonitrile porphyrin can be synthesized by the condensation reaction of porphyrin aldehyde and diaminomalonitrile as shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

As in Reaction Scheme 1 above, the present invention provides a process for preparing the compound, comprising the steps of:

(i) reacting 5- (4'-hydroxymethylphenyl) -15-phenylporphyrine [5- (4'-hydroxymethylphenyl) -naphthalenesulfonate by reacting benzaldehyde, hydroxymethyl benzaldehyde and dipyromethane, -15-phenyl porphyrin];

(Ii) oxidizing the hydroxyl group of 5- (4'-hydroxymethylphenyl) -15-phenylporphyrin obtained in step (i) to give 5- (4'-formylphenyl) -formylphenyl) -15-phenyl porphyrin]: and

(Iii) reacting 5- (4'-formylphenyl) -15-phenylporphyrin obtained in step (ii) with diaminomaleonitrile (DAMN) 2'-diphenyl-21'H, 23'H-porphin-5'-yl) -methyleneamino] -2-butenidinyl] H, 23'H-porphin-5'-yl) -methyleneamino] -2-butenedinitrile}}.

Step (i) is a step of synthesizing a 5- (4'-hydroxymethylphenyl) -15-phenyl porphyrin of the formula (2) having a porphyrin 5 carbon atom. Benzaldehyde, hydroxymethyl benzaldehyde and dipyyromethane are placed in a dichloromethane solvent, and then a nitrogen atmosphere is prepared. Trifluoroacetic acid (TFA) is used as an acid catalyst to conduct a reaction . The reaction product is obtained by reacting a porphyrin derivative of the formula (1) [5,15-bis (4'-hydroxymethylphenyl) porphyrin] with a porphyrin derivative of the formula (3) together with a porphyrin derivative [5- [5,15-diphenyl porphyrin], and the porphyrin derivative is separated by column chromatography to obtain a porphyrin derivative of the formula (2).

The step (ii) is a step of oxidizing the hydroxyl group of the porphyrin derivative of formula (2) to convert it to an aldehyde group to obtain a porphyrin derivative [5- (4'-formylphenyl) -15-phenyl porphyrin]. A porphyrin derivative of the formula (2), an oxidizing agent (for example, pyridinium chlorochromate (PCC)) is placed in a chloroform solvent (30 ml) and reacted in a nitrogen atmosphere. The obtained product is separated by column chromatography to obtain a porphyrin derivative [5- (4'-formylphenyl) -15-phenyl porphyrin] of the formula (4).

The step (iii) is a condensation reaction of the aldehyde group of the porphyrin derivative of the formula (4) with diaminomalenonitrile (DAMN) to give the final compound [2-amino-3 - [(5 ', 15'-diphenyl -21'H, 23'H-porphin-5'-yl) -methyleneamino] -2-butenedinitrile. A porphyrin derivative (4), DAMN, is added in a dimethylformamide solvent and allowed to react. The obtained product was separated by column chromatography to obtain the porphyrin derivative [2-amino-3 - [(5 ', 15'-diphenyl-21'H, 23'H-porphin-5'- 2-butenedinitrile].

The present invention also provides a composition for detecting mercury ions containing the above compound.

In one embodiment, the composition for mercury ion detection may comprise tetrahydrofuran as a solvent.

The present invention also provides a mercury ion detection method comprising the step of reacting the compound with a sample.

In one embodiment, in the mercury ion detection method, tetrahydrofuran may be used as a solvent.

In the composition for mercury ion detection and the mercury ion detection method, the compound of Chemical Formula 5 increases the absorbance (red shift of the maximum absorption band) in a visible light wavelength range of 400 to 430 nm, particularly 420 nm upon addition of mercury ions, Fluorescence is reduced in the wavelength range of 620 - 710 nm, especially at 632 nm and 696 nm. This is due to the mechanism by which the DAMN group is coordinated with the mercury ion when mercury ions are added to the THF solution in which the DAMN-porphyrin is dissolved.

The fluorescence extinction phenomenon was not observed for other cations, and the selectivity for mercury ions was confirmed, and the mercury ion detection limit of DAMN-porphyrin was measured to be 3.33 x 10 ^-7 M.

Further, the present invention provides a mercury ion detection apparatus using the above compound.

In one embodiment, the mercury ion detection apparatus can use tetrahydrofuran as a solvent, measure absorbance at 400-430 nm in a visible light wavelength range, and measure fluorescence at a fluorescence wavelength range of 620-710 nm.

Hereinafter, the present invention will be described in more detail through examples and test examples. However, the following examples and test examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1. Synthesis of diaminomalonitrile porphyrin compound

(1) Synthesis method

The diaminomaleonitrile porphyrin (DAMN-porphyrin) [2-amino-3 - [(5 ', 15'-diphenyl-21'H, 23'H-porphin-5'- 2-butenedinitrile] was synthesized by the condensation reaction of porphyrin aldehyde and diaminomalonitrile as shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

Specifically, the synthesis process is as follows.

In the above step (i), a porphyrin derivative [5- (4'-hydroxymethylphenyl) -15-phenyl porphyrin] having a reactive group at the 5th carbon of porphyrin was synthesized. (1 equivalent), 2.4 mM (1 equivalent), 4.9 mM (2 equivalents) of benzaldehyde, hydroxymethyl benzaldehyde, and dipyyromethane, respectively, in a dichloromethane solvent Equivalent), and then a nitrogen atmosphere was established. Trifluoroacetic acid (TFA) was used as an acid catalyst in a dark room for 6 hours, then chloranil (1.25 equivalents) was added, and the mixture was stirred for 1 hour. The acid was then neutralized with triethylamine and stirred until completion of the reaction. As a result, a porphyrin derivative [5,15-bis (4'-hydroxymethylphenyl) porphyrin] of formula (1), a porphyrin derivative of formula (3) 5,15-diphenyl porphyrin] was obtained. The porphyrin derivative was isolated using column chromatography (developing solvent: chloroform) to obtain a porphyrin derivative of formula (2) in a yield of 14%.

In the step (ii), the hydroxyl group of the porphyrin derivative of the formula (2) is oxidized to an aldehyde group to synthesize a porphyrin derivative [5- (4'-formylphenyl) -15-phenyl porphyrin]. 15.6 mM (1 equivalent) and 23.4 mM (1.5 equivalents) of a porphyrin derivative of formula (2) and pyridinium chlorochromate (PCC) were added to chloroform solution (30 ml), followed by stirring under nitrogen for 90 minutes Respectively. As a result, a porphyrin derivative [5- (4'-formylphenyl) -15-phenyl porphyrin] was obtained in a yield of 62% using column chromatography (developing solvent: 90% chloroform + 10% hexane).

In the above step (iii), the condensation reaction of the aldehyde group of the porphyrin derivative of formula (4) with diaminomalenonitrile (DAMN) yields the final compound [2-amino-3 - [(5 ', 15'-diphenyl -21'H, 23'H-porphin-5'-yl) -methyleneamino] -2-butenedinitrile. 9 mM (1 equivalent) and 9 mM (1 equivalent) of a porphyrin derivative represented by the formula (4) and DAMN were added to a dimethylformamide solvent (20 ml), and the mixture was stirred for at least 8 hours until completion of the reaction. As a result, a 45% yield of a porphyrin derivative of Formula 5 [2-amino-3 - [(5 ', 15'-diphenyl-21'H, 23'H-porphin-5'-yl) -methyleneamino] -2-butenedinitrile].

(2) Structural analysis

The ¹ H NMR spectrum and the ¹³ C NMR spectrum of the compound of formula (5) (DAMN-porphyrin) in CDCl ₃ are shown in FIGS. 1 and 2, respectively. The MALDI-TOF spectra of the compounds of the formulas (4) and (5) are shown in FIGS. 3 and 4, respectively.

The frontier molecular orbital (LUMO in HOMO) and the optimized structure of DAMN-porphyrin, calculated using the B3LYP level of Density Functional Theory (DFT), are shown in FIG.

Test Example 1. Evaluation of selectivity of DAMN-porphyrin for mercury ion

It showed the effect of various metal ions on the UV- visible spectrum of the compound of formula 5 (3.33 x 10 ^-7 M) in THF in Figure 5, in a THF solvent, Hg (NO ₃₎ using the formula ₂₅ compound (3.33 x 10 <" ⁷ > M) is shown in Fig.

As respectively shown in Figs. 5 and 6, other metal cations (Na ^+, K ^+, Mg ^{2 +,} Ca ^2+, Zn ^{2 +,} Co ^{2 +,} Cu ^{2 +,} Pb ^{2 +,} Ni ^{2 +,} Al ^{3 +} , Cr ^{3 +} ) does not affect the visible light absorbance spectrum of the compound of formula (5), whereas the compound of formula (5) decreases the absorbance at 407 nm and the absorbance at 420 nm by Hg ^{2 +} , Transition of visible light absorption wavelength (transition from red to yellow).

Showed the effect of various metal ions on the fluorescence emission spectra (λ _ex [Excitation wavelength] = 407 nm) in THF formula 5 compound (3.33 x 10 ^-7 M) in a solvent in Figure 7, in a THF solvent, Hg (NO ₃ ) exhibited fluorescence titration spectrum (λ _ex [Excitation wavelength] = 407 nm) of the general formula (V) compound (3.33 x 10 ^-7 M) with a ₂ in Fig.

As respectively shown in Figs. 7 and 8, other metal cations (Na ^+, K ^+, Mg ^{2 +,} Ca ^2+, Zn ^{2 +,} Co ^{2 +,} Cu ^{2 +,} Pb ^{2 +,} Ni ^{2 +,} Al ^{3 +} , Cr ^{3 +} ) do not affect the fluorescence emission spectrum of the compound of Formula 5, whereas the compound of Formula 5 by fluorescence quenching (fluorescence quenching) at 632 nm and 696 nm by Hg ^{2 +} , And mercury ion selectivity.

Test Example 2. Measurement limit of DAMN-porphyrin

Gradual addition of mercury ions to diaminomalonitrile porphyrin in THF resulted in a gradual decrease in fluorescence emission intensity of diaminomalonitrile porphyrin at 632 nm and 695 nm. Reduction of fluorescence intensity of diaminomalonitrile porphyrin by the added mercury ion follows the linear relationship (R ² = 0.993) in the range of Hg ^{2 +} ion concentration of 0.40 μM - 1.86 μM. The detection limit for mercury ions of diaminomalonitrile porphyrin was 1.12 x 10 < ^-8 > M, and the detection limit (LOD) was calculated by the following equation.

[Equation 1]

: 수은 이온 농도 대 세기(intensity) 사이의 기울기)(s: standard deviation of blanket measurement,

: Slope between mercury ion concentration and intensity)

Claims (10)

A compound represented by the following formula (5):
[Chemical Formula 5]

.
(i) reacting benzaldehyde, hydroxymethylbenzaldehyde and dipyrromethane to obtain 5- (4'-hydroxymethylphenyl) -15-phenylporphyrin;
(Ii) oxidizing the hydroxyl group of 5- (4'-hydroxymethylphenyl) -15-phenylporphyrin obtained in step (i) to obtain 5- (4'-formylphenyl) -15-phenylporphyrin; and
(Iii) reacting 5- (4'-formylphenyl) -15-phenylporphyrin obtained in step (ii) with diaminomalenonitrile to obtain 2-amino-3 - [(5 ', 15'- 21'H, 23'H-porphine-5'-yl) -methyleneamino] -2-butenediitrile]
Lt; RTI ID = 0.0 > 1. ≪ / RTI >
A composition for detecting mercury ions, comprising the compound of claim 1.
The composition for detecting mercury ions according to claim 3, which comprises tetrahydrofuran as a solvent.
A method for detecting mercury ions, comprising the step of reacting the compound of claim 1 with a sample.
6. The mercury ion detection method according to claim 5, wherein tetrahydrofuran is used as a solvent.
6. The method of claim 5, comprising measuring the absorbance at 400-430 nm in a visible light wavelength range and measuring fluorescence at a fluorescence wavelength range of 620-710 nm.
A mercury ion detection device using the compound of claim 1.
The mercury ion detection apparatus according to claim 8, wherein tetrahydrofuran is used as a solvent.
9. The mercury-ion detecting apparatus according to claim 8, wherein the absorbance is measured at a wavelength range of 400 to 430 nm and the fluorescence is measured at a fluorescence wavelength range of 620 to 710 nm.

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